Haiogenibes op  aromatic oxaminic acibs



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rosnn MEIER, UF WIJESDORF, NEAR COLOGNE-QN-THJE-RHINE, GERMANY, ASSIGNOR T01 GAS$ELLI DTJEST'UJFJE CORPORATION, OF NEW YORK, N. Y., A. CORPORATION OF i lElUGrlENIlDES 0F AROMA'JLTC OXAIVTINIC ACIJDS.

lilo hrawlna'. Application filed November 26, 19%, Serial 11' o. 151,006,.ani1 in Germany November 25, 1925.

The present invention relates to processes for the production of aromatic oxaminic acid halogenides, andto certain new products obtainable thereby. I

Halogenides of aromatic oxaminic acids derived from primary aromatic amines could, heretofore, only be produced with difiticult (see Berichte d. Deutschen Chem. Ges. vo I 23, page 1823, (1890) a The action of oxalylchloride upon secondary bases, such as monoethylaniline or diphenylamine, produces'the halogenides of the corresponding oxaminic acids; with free primary bases, such as aniline or the naphthylamines, the action ofoxalylhalogenides does not lead to the desired results." I

T have discovered that by reacting with oralylhalogenides upon the saltsof aromatic primary amines there are produced the halogenides of the corresponding oramlnic acids.

The reaction can be performed, particularly in the case of the chloride, with a small .or a large excess of the chloride or the presence or absence of an .indlderentdiluent, or solvent. The resulting oxaminic chlorides usually separate in crystalline form" 111 in stances where they are moreor less soluble in the diluent it is possible to precipitate them by the addition of petrolehmethene reaction usually proceeds at ordinary temperature, i. e., at a temperature of from about 10 to about Tu certain casesitmay be advisable to induce the reaction by slight heating, i. e., to a temperature of about 10" 1]., as for instance in the preparation of the new o-toluyloxaminic acid chloride, ob-.

tained, by practicing the process accorg to the present invention, as yellow-needles-have ing the melting point of 89-90" U; or of the,

new alphanaphthyl-oaaminic acid chloride (occurring in the crystalline form as yellowish needles, melting at 86 G.) etc. I

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lid process is particularly applicable to th pro action of the chlorides of aromatic onaminic acids. 1 I

The following examples will further illustrate my invention, the parts being by weight.

- Example 1.50 parts of finely ground aniline hydrochloride. are quickly introduced at, ordinary temperature (i. e., 15-d0 0.).1nto

200 parts of well stirred oxalylchloride. \The aniline salt dissolves at first with violent evolution cit-hydrochloric acid gas, but soon the der reduced pressure and the residue crystalllzed from ligroin; the known phenyl oxam inic acid chloride of the formula ONE-CO-CO-Cl is obtained. It melts at 8285 G, in accordance with the statements in the literature. The yield is nearly quantitative.

, Example 2.100 parts of beta-naphthylamine hydrochloride are suspended in iOO parts of chlorobenzene and at about 10 C.

.100 parts of oxalylchloride are added. The

of hydrochloric acid gas beginning at about 15 C. The resulting oxaminic acid chloride starts to separate from the reaction mass after some stirring at room temperature.

After the evolution of hydrochloric acid gas has ceased, petroleumether is added to com lets. the precipitation. The new betanap}l thyl-onarninic acid chloride of the formu a Y NEI-OO-OOwCl is so obtained. Crystallization from UGIIZGDB produces it as nearly colorless, soft needles,-

melting with decompositon at lit-115 C.

Example .3.50 parts of Schloro-l-naph thylamine hydrochloride are susgended in i 200 parts of nitrobenzene andat a cut from 5-10" (3., parts of oxalylchloride are added. The mass is well stirred and the temperature; allowed to increase. slowly to about C. After cooling ligroine is added to precipitate the new e-chloro-l-naphthylamine oxaminic acid chloride in the form of colorless needles melting at 161 C.

The new e-methoxy-l-naphthyl oxaminic acid chloride obtained in an analogous way crystallizes from chloro-benzene in yellow needles melting at 172- C. p

Tnstead of isolating the oxaminic acid chloride as describedabove, it is also possible to separate it from the excess oxalylchloride by distillinf it ed with the chlorobenzene solu tion un er reduced pressure; the so obtained ltlt) 1. In processes for the production of an "oxaminic acid halogenide of a'primary aromaticamine, the'step consisting in reacting with an oxalylhalogenideupon a salt of a primary aromatic amine. I

2. In processes for-the production of an oxaminic acid chloride of a primary aromatic amine, the step consisting n reacting with oxalylchloride upon a salt of a primary aromatic amine.

3. In processes for the production of an oxaminie acid chloride of a primary aromatic amine, the step consisting in reacting with oxalylchloride upon the hydrochloride of a primary aromatic amine. 1 4. In processes for the production of an oxaminic acid hloride of a primary aromatic amine,-the ste consisting in reacting, at a. temperature 0 from about 1 0 to about (3., with oxalylchloride upon the hydrochloride of a primary aromatic amine.

5. Process for the reduction of-an aryl oxaminic acid 'chlori e of the naphthalene series which comprises reacting with oizalylchloride upon a ydrochloride of a primary naphthylamine. compound.

6. As new articles of manufacture oxaminic acid halogenides of the naphthalene series being solid products splitting ofi hydrogen-halide upon treatment with water.

7. As new articles 'of manufacture oxaminic acid chlorides of the naphthalene series being solid products splitting ofi hydrochloric acid upon treatment with water.

8. As new products, the compounds of the general formula:

X NH-CO-CO-Clwherein X stands for one of the substituents chlorine and methoxy.

9. Y As a new product, the compound of the formula:

which forms colorless needles, melting at 161 C.

In testimony whereof, I aflix my signature;

' JOSEF HALLER. 

